Aqueous cleaning composition which may be in microemulsion form containing a silicone antifoam agent

ABSTRACT

An improvement is described in all purpose liquid cleaning composition and microemulsion composition which are especially effective in the removal of oily and greasy soil and contain an anionic detergent, a nonionic surfactant and ethoxylated polyhydric alcohol type compound, a cosurfactant, a hydrocarbon ingredient, a silicone antifoam agent, and water.

RELATED APPLICATION

This application is a continuation-in-part application of U.S. Ser. No.08/999,674 filed Jun. 23, 1997, now abandoned, which in turn is acontinuation in part application of U.S. Ser. No. 8/698,606 filed Aug.16, 1996, now U.S. Pat. No. 5,776,880 which in turn is a continuation inpart application of U.S. Ser. No. 8/336,936 filed Nov. 15, 1994, nowU.S. Pat. No. 5,549,840 which in turn is a continuation-in-partapplication of U.S. Ser. No. 8/192,118 filed Feb. 3, 1994, now abandonedwhich in turn is a continuation-in-part application of U.S. Ser. No.8/155,317 filed Nov. 22, 1993, now abandoned which is acontinuation-in-part application of U.S. Ser. No. 8/102,314 filed Aug.4, 1993, now abandoned.

FIELD OF THE INVENTION

The present invention relates to a quick drying surface liquid cleaningcomposition.

BACKGROUND OF THE INVENTION

This invention relates to an improved all-purpose liquid cleaningcomposition or a microemulsion composition having improved drying timesdesigned in particular for cleaning hard surfaces and which is effectivein removing grease soil and/or bath soil and in leaving unrinsedsurfaces with a shiny appearance.

In recent years all-purpose liquid detergents have become widelyaccepted for cleaning hard surfaces, e.g., painted woodwork and panels,tiled walls, wash bowls, bathtubs, linoleum or tile floors, washablewall paper, etc. Such all-purpose liquids comprise clear and opaqueaqueous mixtures of water-soluble synthetic organic detergents andwater-soluble detergent builder salts. In order to achieve comparablecleaning efficiency with granular or powdered all-purpose cleaningcompositions, use of water-soluble inorganic phosphate builder salts wasfavored in the prior art all-purpose liquids. For example, such earlyphosphate-containing compositions are described in U.S. Pat. Nos.2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.

In view of the environmentalist's efforts to reduce phosphate levels inground water, improved all-purpose liquids containing reducedconcentrations of inorganic phosphate builder salts or non-phosphatebuilder salts have appeared. A particularly useful self-opacified liquidof the latter type is described in U.S. Pat. No. 4,244,840.

However, these prior art all-purpose liquid detergents containingdetergent builder salts or other equivalent tend to leave films, spotsor streaks on cleaned unrinsed surfaces, particularly shiny surfaces.Thus, such liquids require thorough rinsing of the cleaned surfaceswhich is a time-consuming chore for the user.

In order to overcome the foregoing disadvantage of the prior artall-purpose liquid, U.S. Pat. No. 4,017,409 teaches that a mixture ofparaffin sulfonate and a reduced concentration of inorganic phosphatebuilder salt should be employed.

However, such compositions are not completely acceptable from anenvironmental point of view based upon the phosphate content. On theother hand, another alternative to achieving phosphate-free all-purposeliquids has been to use a major proportion of a mixture of anionic andnonionic detergents with minor amounts of glycol ether solvent andorganic amine as shown in U.S. Pat. No. 3,935,130. Again, this approachhas not been completely satisfactory and the high levels of organicdetergents necessary to achieve cleaning cause foaming which, in turn,leads to the need for thorough rinsing which has been found to beundesirable to today's consumers.

Another approach to formulating hard surfaced or all-purpose liquiddetergent composition where product homogeneity and clarity areimportant considerations involves the formation of oil-in-water (o/w)microemulsions which contain one or more surface-active detergentcompounds, a water-immiscible solvent (typically a hydrocarbon solvent),water and a "cosurfactant" compound which provides product stability. Bydefinition, an o/w microemulsion is a spontaneously forming colloidaldispersion of "oil" phase particles having a particle size in the rangeof 25 to 800 Å in a continuous aqueous phase.

In view of the extremely fine particle size of the dispersed oil phaseparticles, microemulsions are transparent to light and are clear andusually highly stable against phase separation.

Patent disclosures relating to use of grease-removal solvents in o/wmicroemulsions include, for example, European Patent Applications EP0137615 and EP 0137616--Herbots et al; European Patent Application EP0160762--Johnston et al; and U.S. Pat. No. 4,561,991--Herbots et al.Each of these patent disclosures also teaches using at least 5% byweight of grease-removal solvent.

It also is known from British Patent Application GB 2144763A to Herbotset al, published Mar. 13, 1985, that magnesium salts enhancegrease-removal performance of organic grease-removal solvents, such asthe terpenes, in o/w microemulsion liquid detergent compositions. Thecompositions of this invention described by Herbots et al. require atleast 5% of the mixture of grease-removal solvent and magnesium salt andpreferably at least 5% of solvent (which may be a mixture ofwater-immiscible non-polar solvent with a sparingly soluble slightlypolar solvent) and at least 0.1% magnesium salt.

However, since the amount of water immiscible and sparingly solublecomponents which can be present in an o/w microemulsion, with low totalactive ingredients without impairing the stability of the microemulsionis rather limited (for example, up to 18% by weight of the aqueousphase), the presence of such high quantities of grease-removal solventtend to reduce the total amount of greasy or oily soils which can betaken up by and into the microemulsion without causing phase separation.

The following representative prior art patents also relate to liquiddetergent cleaning compositions in the form of o/w microemulsions: U.S.Pat. No. 4,472,291 - Rosario; U.S. Pat. No. 4,540,448 - Gauteer et al;U.S. Pat. No. 3,723,330 - Sheflin; etc.

Liquid detergent compositions which include terpenes, such asd-limonene, or other grease-removal solvent, although not disclosed tobe in the form of o/w microemulsions, are the subject matter of thefollowing representative patent documents: European Patent Application0080749; British Patent Specification 1,603,047; and U.S. Pat. Nos.4,414,128 and 4,540,505. For example, U.S. Pat. No. 4,414,128 broadlydiscloses an aqueous liquid detergent composition characterized by, byweight:

(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric orzwitterionic surfactant or mixture thereof;

(b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, ata weight ratio of (a):(b) being in the range of 5:1 to 1:3; and

(c) from 0.5% 10% of a polar solvent having a solubility in water at 15°C. in the range of from 0.2% to 10%. Other ingredients present in theformulations disclosed in this patent include from 0.05% to 2% by weightof an alkali metal, ammonium or alkanolammonium soap of a C₁₃ -C₂₄ fattyacid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueoussolvent, e.g., alcohols and glycol ethers, up to 10% by weight; andhydrotropes, e.g., urea, ethanolamines, salts of lower alkylarylsulfonates, up to 10% by weight. All of the formulations shown in theExamples of this patent include relatively large amounts of detergentbuilder salts which are detrimental to surface shine.

Furthermore, the present inventors have observed that in formulationscontaining grease-removal assisting magnesium compounds, the addition ofminor amounts of builder salts, such as alkali metal polyphosphates,alkali metal carbonates, nitrilotriacetic acid salts, and so on, tendsto make it more difficult to form stable microemulsion systems.

SUMMARY OF THE INVENTION

The present invention provides an improved, quick drying surface, liquidcleaning composition having improved interfacial tension which improvescleaning hard surface in the form of a microemulsion which is suitablefor cleaning hard surfaces such as plastic, vitreous and metal surfaceshaving a shiny finish, oil stained floors, automotive engines and otherengines. More particularly, the improved cleaning compositions, improveddrying times and exhibit good grease soil removal properties due to theimproved interfacial tensions, when used in undiluted (neat) form andleave the cleaned surfaces shiny without the need of or requiring onlyminimal additional rinsing or wiping. The latter characteristic isevidenced by little or no visible residues on the unrinsed cleanedsurfaces and, accordingly, overcomes one of the disadvantages of priorart products.

Surprisingly, these desirable results are accomplished even in theabsence of polyphosphate or other inorganic or organic detergent buildersalts and also in the complete absence or substantially complete absenceof grease-removal solvent.

In one aspect, the invention generally provides a stable, opticallyclear microemulsion, hard surface cleaning composition especiallyeffective in the removal of oily and greasy oil, which is in the form ofa substantially dilute oil-in-water microemulsion having an aqueousphase and an oil phase; The dilute microemulsion composition includes,on a weight basis:

0.1% to 20% of an anionic surfactant;

0.1% to 15% of a cosurfactant;

0.1% to 10% of an ethoxylated polyhydric alcohol type compound (asdefined below);

0.1% to 10% of an ethoxylated nonionic surfactant;

0.01% to 0.2% of a silicone antifoam agent which is a polyalkyleneoxidimethyl siloxane, wherein the alkylene group has 2 to 40 carbonatoms;

0 to 15% of magnesium sulfate heptahydrate;

0.4 to 10.0% of a perfume, essential oil, or water insoluble hydrocarbonhaving 6 to 18 carbon atoms; and

the balance being water.

In a second aspect, the invention comprises an all purpose hard surfacecleaning composition comprising approximately by weight:

0.1% to 20% of an anionic surfactant;

0.1% to 15% of a cosurfactant;

0.1% to 10% of an ethoxylated nonionic surfactant;

0.1% to 10% of an ethoxylated polyhydric alcohol type compound (asdefined below);

0.01% to 0.2% of a silicone antifoam agent which is a polyalkyleneoxidimethyl siloxane wherein the alkylene group has 2 to 40 carbonatoms;

0 to 15% of magnesium sulfate heptahydrate;

0 to 10%, more preferably 0.1% to 10% of a perfume, essential oil orwater insoluble hydrocarbon having 6 to 18 carbon atoms; and

the balance being water.

The instant microemulsion and all purpose cleaning composition of theinstant invention do not contain a fatty acid or an alkali metal salt ofa fatty acid (fatty acid soap), or a C₄₋₁₂ alcohol ester of asulfosuccinic acid salt and the compositions are pourable and have astorage modulus of less than 0.5 Pascal (0.5 Newton/sg. m.), whenmeasured at 25° C., at a frequency of ten radians/second and a strain of0.01 and the compositions are not liquid crystals.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates a graph of the drying times of Formulas A to D.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a stable optically clear microemulsioncomposition comprising approximately by weight: 0.1% to 20% of ananionic surfactant, 0.1% to 15% of a cosurfactant; 0.1% to 10% of anethoxylated polyhydric alcohol type compound, 0.1% to 10% of anethoxylated nonionic surfactant; 0.01% to 0.2% of a silicone antifoamagent which is a polyalkylene oxidimethyl siloxane such as TP305manufactured by OSI Specialties which is Witco Chemical, Co.; 0.4% to10% of a water insoluble hydrocarbon, essential oil or a perfume and thebalance being water.

According to the present invention, the role of the water insolublehydrocarbon can be provided by a non-water-soluble perfume. Typically,in aqueous based compositions the presence of a solubilizers, such asalkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine,urea, etc., is required for perfume dissolution, especially at perfumelevels of 1% and higher, since perfumes are generally a mixture offragrant essential oils and aromatic compounds which are generally notwater-soluble. Therefore, by incorporating the perfume into the aqueouscleaning composition as the oil (hydrocarbon) phase of the ultimate o/wmicroemulsion composition, several different important advantages areachieved.

As used herein and in the appended claims the term "perfume" is used inits ordinary sense to refer to and include any non-water solublefragrant substance or mixture of substances including natural (i.e.,obtained by extraction of flower, herb, blossom or plant), artificial(i.e., mixture of natural oils or oil constituents) and syntheticallyproduced substance) odoriferous substances. Typically, perfumes arecomplex mixtures of blends of various organic compounds such asalcohols, aldehydes, ethers, aromatic compounds and varying amounts ofessential oils (e.g., terpenes) such as from 0% to 80%, usually from 10%to 70% by weight, the essential oils themselves being volatileodoriferous compounds and also serving to dissolve the other componentsof the perfume.

In the present invention the precise composition of the perfume is of noparticular consequence to cleaning performance so long as it meets thecriteria of water immiscibility and having a pleasing odor. Naturally,of course, especially for cleaning compositions intended for use in thehome, the perfume, as well as all other ingredients, should becosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.. Theinstant compositions show a marked improvement in ecotoxocity ascompared to existing commercial products.

The hydrocarbon such as a perfume is present in the dilute o/wmicroemulsion in an amount of from 0 to 10% by weight, preferably from0.4% to 10% by weight, especially preferably from 0.5% to 6% by weight.If the amount of hydrocarbon (perfume) is less than 0.4% by weight itbecomes difficult to form the o/w microemulsion. If the hydrocarbon(perfume) is added in amounts more than 10% by weight, the cost isincreased without any additional cleaning benefit and, in fact, withsome diminishing of cleaning performance insofar as the total amount ofgreasy or oily soil which can be taken up in the oil phase of themicroemulsion will decrease proportionately. In the all purpose hardsurface cleaning composition which is not a microemulsion theconcentration of the perfume is 0 to 10 wt. %, more preferably 0.1 wt. %to 10 wt. %

In place of the perfume in either the microemulsion composition or theall purpose hard surface cleaning composition at the same previouslydefined concentrations that the perfume was used in either themicroemulsion or the all purpose hard surface cleaning composition onecan employ an essential oil or a water insoluble hydrocarbon having 6 to18 carbon such as a paraffin or isoparaffin.

Suitable essential oils are selected from the group consisting of:Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand,Balsam (Peru), Basil oil (India), Black pepper oil, Black pepperoleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China),Camphor oil, White, Camphor powder synthetic technical, Cananga oil(Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP,Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil,Clove leaf, Coriander (Russia), Coumarin 69° C. (China), CyclamenAldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil,Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Gingeroleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam,Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil,L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oildistilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methylcedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Muskketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermintoil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin,Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmintoil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java),Wintergreen

Regarding the anionic surfactant present in the o/w microemulsions anyof the conventionally used water-soluble anionic surfactants or mixturesof said anionic surfactants and anionic surfactants can be used in thisinvention. As used herein the term "anionic surfactant" is intended torefer to the class of anionic and mixed anionic-nonionic detergentsproviding detersive action.

The water-soluble organic surfactant materials which are used in formingthe ultimate o/w microemulsion compositions of this invention may beselected from the group consisting of water-soluble, non-soap, anionicsurfactants mixed with a fatty acid and a partially esterfiedethoxylated glycerol.

Suitable water-soluble non-soap, anionic surfactants include thosesurface-active or detergent compounds which contain an organichydrophobic group containing generally 8 to 26 carbon atoms andpreferably 10 to 18 carbon atoms in their molecular structure and atleast one water-solubilizing group selected from the group of sulfonate,sulfate and carboxylate so as to form a water-soluble detergent.Usually, the hydrophobic group will include or comprise a C₈ -C₂₂ alkyl,alkyl or acyl group. Such surfactants are employed in the form ofwater-soluble salts and the salt-forming cation usually is selected fromthe group consisting of sodium, potassium, ammonium, magnesium andmono-, di- or tri-C₂ -C₃ alkanolammonium, with the sodium, magnesium andammonium cations again being preferred.

Examples of suitable sulfonated anionic surfactants are the well knownhigher alkyl mononuclear aromatic sulfonates such as the higher alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the higheralkyl group in a straight or branched chain, C₈ -C₁₅ alkyl toluenesulfonates and C₈ -C₁₅ alkyl phenol sulfonates.

One preferred sulfonate surfactant is a linear alkyl benzene sulfonatehaving a high content of 3- (or higher) phenyl isomers and acorrespondingly low content (well below 50%) of 2- (or lower) phenylisomers, that is, wherein the benzene ring is preferably attached inlarge part at the 3 or higher (for example, 4, 5, 6 or 7) position ofthe alkyl group and the content of the isomers in which the benzene ringis attached in the 2 or 1 position is correspondingly low. Particularlypreferred materials are set forth in U.S. Pat. No. 3,320,174.

Other suitable anionic surfactants are the olefin sulfonates, includinglong-chain alkene sulfonates, long-chain hydroxyalkane sulfonates ormixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefinsulfonate detergents may be prepared in a known manner by the reactionof sulfur trioxide (SO₃) with long-chain olefins containing 8 to 25,preferably 12 to 21 carbon atoms and having the formula RCH=CHR₁ where Ris a higher alkyl group of 6 to 23 carbons and R₁ is an alkyl group of 1to 17 carbons or hydrogen to form a mixture of sultones and alkenesulfonic acids which is then treated to convert the sultones tosulfonates. Preferred olefin sulfonates contain from 14 to 16 carbonatoms in the R alkyl group and are obtained by sulfonating analpha-olefin.

Other example of operative anionic surfactants includes sodium dioctylsulfosuccinate di-(2 ethylhexyl) sodium sulfosuccinate being one! andcorresponding dihexyl and dioctyl esters. The preferred sulfosuccinicacid ester salts are esters of aliphitic alcohols such as saturatedalkanols of 4 to 12 carbon atoms and are normally diesters of suchalkanols. More preferably such are alkali metal salts of the diesters ofalcohols of 6 to 10 carbons atoms and more preferably the diesters willbe from octanol, such as 2-ethyl hexanol, and the sulfonic acid saltwill be the sodium salt.

Especially preferred anionic sulfonate surfactants are paraffinsulfonates containing 10 to 20, preferably 13 to 17, carbon atoms.Primary paraffin sulfonates are made by reacting long-chain alphaolefins and bisulfites and paraffin sulfonates having the sulfonategroup distributed along the paraffin chain are shown in U.S. Pat. Nos.2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.

Examples of satisfactory anionic sulfate surfactants are the C₈ -C₁₈alkyl sulfate salts and the ethoxylated C₈ -C₁₈ alkyl ether sulfatesalts having the formula R(OC₂ H₄)_(n) OSO₃ M wherein n is 1 to 12,preferably 1 to 5, and M is a solubilizing cation selected from thegroup consisting of sodium, potassium, ammonium, magnesium and mono-,di- and triethanol ammonium ions. The alkyl sulfates may be obtained bysulfating the alcohols obtained by reducing glycerides of coconut oil ortallow or mixtures thereof and neutralizing the resultant product.

On the other hand, the alkyl ether polyethenoxy sulfates are obtained bysulfating the condensation product of ethylene oxide with a C₈ -C₁₈alkanol and neutralizing the resultant product. The alkyl etherpolyethenoxy sulfates differ from one another in the number of moles ofethylene oxide reacted with one mole of alkanol. Preferred alkylsulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to16 carbon atoms in the alkyl group.

The ethoxylated C₈ -C₁₂ alkylphenyl ether sulfates containing from 2 to6 moles of ethylene oxide in the molecule also are suitable for use inthe inventive compositions. These surfactants can be prepared byreacting an alkyl phenol with 2 to 6 moles of ethylene oxide andsulfating and neutralizing the resultant ethoxylated alkyl phenol.

Other suitable anionic detergents are the C₉ -C₁₅ alkyl etherpolyethenoxyl carboxylates having the structural formula R(OC₂ H₄)_(n)OX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X isselected from the group consisting of CH₂, C(O)R₁ and ##STR1## whereinR₁ is a C₁ -C₃ alkylene group. Preferred compounds include C₉ -C₁₁ alkylether polyethenoxy (7-9) C(O) CH₂ CH₂ COOH, C₁₃ -C₁₅ alkyl etherpolyethenoxy (7-9) ##STR2## and C₁₀ -C₁₂ alkyl ether polyethenoxy (5-7)CH₂ COOH. These compounds may be prepared by condensing ethylene oxidewith appropriate alkanol and reacting this reaction product withchloracetic acid to make the ether carboxylic acids as shown in U.S.Pat. No. 3,741,911 or with succinic anhydride or phtalic anhydride.

Obviously, these anionic surfactants will be present either in acid formor salt form depending upon the pH of the final composition, with thesalt forming cation being the same as for the other anionic detergents.

Of the foregoing non-soap anionic sulfonate surfactants, the preferredsurfactants are the magnesium salt of the C₁₃ -C₁₇ paraffin or alkanesulfonates.

Generally, the proportion of the nonsoap-anionic surfactant will be inthe range of 0.1% to 20.0%, preferably from 1% to 15%, by weight of thedilute o/w microemulsion composition or the all purpose hard surfacecleaning composition.

The instant composition contains a composition (herein after refered toas an ethoxylated polyhydric alcohol type compound such as anethoxylated glycerol type compound) which is a mixture of a fullyesterified ethoxylated polyhydric alcohol, a partially esterifiedethoxylated polyhydric alcohol and a nonesterified ethoxylatedpolyhydric alcohol, wherein the preferred polyhydric alcohol isglycerol, and the compound is ##STR3## wherein w equals one to four,most preferably one, and B is selected from the group consisting ofhydrogen or a group represented by: ##STR4## wherein R is selected fromthe group consisting of alkyl group having 6 to 22 carbon atoms, morepreferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22carbon atoms, more preferably 11 to 15 carbon atoms, wherein ahydrogenated tallow alkyl chain or a coco alkyl chain is most preferred,wherein at least one of the B groups is represented by said ##STR5## andR' is selected from the group consisting of hydrogen and methyl groups;x, y and z have a value between 0 and 60, more preferably 0 to 40,provided that (x+y+z) equals 2 to 100, preferably 4 to 24 and mostpreferably 4 to 19, wherein in Formula (I) the weight ratio ofmonoester/diester/triester is 40 to 90/5 to 35/1 to 20, more preferably50 to 90/9 to 32/1 to 12, wherein the weight ratio of Formula (I) toFormula (II) is a value between 3 to 0.02, preferably 3 to 0.1, mostpreferably 1.5 to 0.2, wherein it is most preferred that there is moreof Formula (II) than Formula (I) in the mixture that forms the compound.

The ethoxylated glycerol type compound used in the instant compositionis manufactured by the Kao Corporation and sold under the trade nameLevenol such as Levenol F-200 which has an average EO of 6 and a molarratio of coco fatty acid to glycerol of 0.55 or Levenol V501/2 which hasan average EO of 17 and a molar ratio of tallow fatty acid to glycerolof 1.0. It is preferred that the molar ratio of the fatty acid toglycerol is less than 1.7, more preferably less than 1.5 and mostpreferably less than 1.0. The ethoxylated glycerol type compound has amolecular weight of 400 to 1600, and a pH (50 grams/liter of water) of5-7. The Levenol compounds are substantially non irritant to human skinand have a primary biodegradabillity higher than 90% as measured by theWickbold method Bias-7d.

Two examples of the Levenol compounds are Levenol V-501/2 which has 17ethoxylated groups and is derived from tallow fatty acid with a fattyacid to glycerol ratio of 1.0 and a molecular weight of 1465 and LevenolF-200 has 6 ethoxylated groups and is derived from coco fatty acid witha fatty acid to glycerol ratio of 0.55. Both Levenol F-200 and LevenolV-501/2 are composed of a mixture of Formula (I) and Formula (II). TheLevenol compounds has ecoxicity values of algae growth inhibition>100mg/liter; acute toxicity for Daphniae>100 mg/liter and acute fishtoxicity>100 mg/liter. The Levenol compounds have a readybiodegradability higher than 60% which is the minimum required valueaccording to OECD 301 B measurement to be acceptably biodegradable.

Polyesterified nonionic compounds also useful in the instantcompositions are Crovol PK-40 and Crovol PK-40 manufactured by CrodaGMBH of the Netherlands. Crovol PK-40 is a polyoxyethylene (12) PalmKernel Glyceride which has 12 EO groups. Crovol PK-70 which is preferredis a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups.

The water soluble ethoxylated nonionic surfactants which can be utilizedin this invention are commercially well known and include the primaryaliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates,alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensateson primary alkanols, such a Plurafacs (BASF) and condensates of ethyleneoxide with sorbitan fatty acid esters such as the Tweens (ICI). Thenonionic synthetic organic detergents generally are the condensationproducts of an organic aliphatic or alkyl aromatic hydrophobic compoundand hydrophilic ethylene oxide groups. Practically any hydrophobiccompound having a carboxy, hydroxy, amido, or amino group with a freehydrogen attached to the nitrogen can be condensed with ethylene oxideor with the polyhydration product thereof, polyethylene glycol, to forma water soluble nonionic detergent.

The nonionic detergent class includes the condensation products of ahigher alcohol (e.g., an alkanol containing about 8 to 18 carbon atomsin a straight or branched chain configuration) condensed with about 5 to30 moles of ethylene oxide, for example, lauryl or myristyl alcoholcondensed with about 16 moles of ethylene oxide (EO), tridecanolcondensed with 6 to moles of EO, myristyl alcohol condensed with about10 moles of EO per mole of myristyl alcohol, the condensation product ofEO with a cut of coconut fatty alcohol containing a mixture of fattyalcohols with alkyl chains varying from 10 to about 14 carbon atoms inlength and wherein the condensate contains either about 6 moles of EOper mole of total alcohol or about 9 moles of EO per mole of alcohol andtallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.

A preferred group of the foregoing nonionic surfactants are the Neodolethoxylates (Shell Co.), which are higher aliphatic, primary alcoholcontaining about 9-15 carbon atoms, such as C₉ -C₁₁ alkanol condensedwith 8 moles of ethylene oxide (Neodol 91-8), C₁₂₋₁₃ alkanol condensedwith 6.5 moles ethylene oxide (Neodol 23-6.5), C₁₂₋₁₅ alkanol condensedwith 12 moles ethylene oxide (Neodol 25-12), C₁₄₋₁₅ alkanol condensedwith 13 moles ethylene oxide (Neodol 45-13), and the like. Suchethoxamers have an HLB (hydrophobic lipophilic balance) value of 8 to 15and give good O/W emulsification, whereas ethoxamers with HLB valuesbelow 8 contain less than 5 ethyleneoxide groups and tend to be pooremulsifiers and poor detergents.

Additional satisfactory water soluble alcohol ethylene oxide condensatesare the condensation products of a secondary aliphatic alcoholcontaining 8 to 18 carbon atoms in a straight or branched chainconfiguration condensed with 5 to 30 moles of ethylene oxide. Examplesof commercially available nonionic detergents of the foregoing type areC₁₁ -C₁₅ secondary alkanol condensed with either 9 EO (Tergitol 15-S-9)or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.

Other suitable nonionic detergents include the polyethylene oxidecondensates of one mole of alkyl phenol containing from 8 to 18 carbonatoms in a straight- or branched chain alkyl group with 5 to 30 moles ofethylene oxide. Specific examples of alkyl phenol ethoxylates includenonyl condensed with 9.5 moles of EO per mole of nonyl phenol, dinonylphenol condensed with 12 moles of EO per mole of dinonyl phenol, dinonylphenol condensed with 15 moles of EO per mole of phenol anddiisoctylphenol condensed with 15 moles of EO per mole of phenol.Commercially available nonionic surfactants of this type include IgepalCO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.

Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- andtri-C₁₀ -C₂₀ alkanoic acid esters having a HLB of 8 to 15 also may beemployed as the nonionic detergent ingredient in the described shampoo.These surfactants are well known and are available from ImperialChemical Industries under the Tween trade name. Suitable surfactantsinclude polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4)sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate andpolyoxyethylene (20) sorbitan tristearate. The silicone antifoam agentswhich are used at a concentration of about 0.01 wt. % to about 0.2 wt.%, more preferably about 0.025 wt. % to about 0.1 wt. % are siloxanessuch as polydimethyl siloxane (TP305 manufactured by OSI Specialties),polyalkylene oxide methyl siloxane and a mixture of polyglycol andsiloxane.

The major class of compounds found to provide highly suitablecosurfactants for the microemulsion over temperature ranges extendingfrom 5° C. to 43° C. for instance are water-soluble polyethylene glycolshaving a molecular weight of 150 to 1000, polypropylene glycol of theformula HO(CH₃ CHCH₂ O)_(n) H wherein n is a number from 2 to 18,mixtures of polyethylene glycol and polypropylene glycol (Synalox) andmono and di C₁ -C₆ alkyl ethers and esters of ethylene glycol andpropylene glycol having the structural formulas R(X)_(n) OH, R₁ (X)_(n)OH, R(X)_(n) OR and R₁ (X)_(n) OR₁ wherein R is C₁ -C₆ alkyl group, R₁is C₂ -C₄ acyl group, X is (OCH₂ CH₂) or (OCH₂ (CH₃)CH) and n is anumber from 1 to 4, diethylene glycol, triethylene glycol, an alkyllactate, wherein the alkyl group has 1 to 6 carbon atoms, 1methoxy-2-propanol, 1 methoxy-3-propanol, and 1 methoxy 2-, 3- or4-butanol.

Representative members of the polypropylene glycol include dipropyleneglycol and polypropylene glycol having a molecular weight of 150 to1000, e.g., polypropylene glycol 400. Other satisfactory glycol ethersare ethylene glycol monobutyl ether (butyl cellosolve), diethyleneglycol monobutyl ether (butyl carbitol), triethylene glycol monobutylether, mono, di, tri propylene glycol monobutyl ether, tetraethyleneglycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether,propylene glycol monomethyl ether, ethylene glycol monohexyl ether,diethylene glycol monohexyl ether, propylene glycol tertiary butylether, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethylene glycol monopropyl ether, ethylene glycol monopentylether, diethylene glycol monomethyl ether, diethylene glycol monoethylether, diethylene glycol monopropyl ether, diethylene glycol monopentylether, triethylene glycol monomethyl ether, triethylene glycol monoethylether, triethylene glycol monopropyl ether, triethylene glycolmonopentyl ether, triethylene glycol monohexyl ether, mono, di,tripropylene glycol monoethyl ether, mono, di tripropylene glycolmonopropyl ether, mono, di, tripropylene glycol monopentyl ether, mono,di, tripropylene glycol monohexyl ether, mono, di, tributylene glycolmono methyl ether, mono, di, tributylene glycol monoethyl ether, mono,di, tributylene glycol monopropyl ether, mono, di, tributylene glycolmonobutyl ether, mono, di, tributylene glycol monopentyl ether and mono,di, tributylene glycol monohexyl ether, ethylene glycol monoacetate anddipropylene glycol propionate. When these glycol type cosurfactants areat a concentration of about 1.0 to about 14 weight %, more preferablyabout 2.0 weight % to about 10 weight % in combination with a waterinsoluble hydrocarbon which is at a concentration of at least 0.5 weight%, more preferably 1.5 weight % one can form a microemulsioncomposition.

While all of the aforementioned glycol ether compounds provide thedescribed stability, the most preferred cosurfactant compounds of eachtype, on the basis of cost and cosmetic appearance (particularly odor),are dipropylene glycol monomethyl ether and diethylene glycol monobutylether. Other suitable water soluble cosurfactants are water solubleesters such as ethyl lactate and water soluble carbohydrates such asbutyl glycosides.

The amount of cosurfactant required to stabilize the microemulsioncompositions will, of course, depend on such factors as the surfacetension characteristics of the cosurfactant, the type and amounts of theprimary surfactants and water insoluble hydrocarbon, and the type andamounts of any other additional ingredients which may be present in thecomposition and which have an influence on the thermodynamic factorsenumerated above. Generally, amounts of cosurfactant in the range offrom 0.1% to 15%, preferably from about 1 wt. % to 10 wt. % providestable dilute o/w microemulsions for the above-described levels ofprimary surfactants and water insoluble hydrocarbon and any otheradditional ingredients as described below.

The amount of cosurfactant required to stabilize the microemulsioncompositions will, of course, depend on such factors as the surfacetension characteristics of the cosurfactant, the type and amounts of theprimary surfactants and perfumes, and the type and amounts of any otheradditional ingredients which may be present in the composition and whichhave an influence on the thermodynamic factors enumerated above.Generally, the amounts of the cosurfactant used in the microemulsion isin the range of from 0.1% to 10%, preferably from 0.5% to 8%, by weightprovide stable dilute o/w microemulsions for the above-described levelsof primary surfactants and perfume and any other additional ingredientsas described below. The amount of cosurfactant in the all purpose hardsurface cleaning composition will be in the range of 0 to 10%, morepreferably 0.1% to 8% by weight.

The ability to formulate neutral and acidic products without builderswhich have grease removal capacities is a feature of the presentinvention because the prior art o/w microemulsion formulations mostusually are highly alkaline or highly built or both.

The final essential ingredient in the inventive microemulsioncompositions having improved interfacial tension properties is water.The proportion of water in the microemulsion or all purpose hard surfacecleaning composition compositions generally is in the range of 20% to97%, preferably 70% to 97% by weight.

As believed to have been made clear from the foregoing description, thedilute 20 o/w microemulsion liquid all-purpose cleaning compositions ofthis invention are especially effective when used as is, that is,without further dilution in water, since the properties of thecomposition as an o/w microemulsion are best manifested in the neat(undiluted) form. However, at the same time it should be understood thatdepending on the levels of surfactants, cosurfactants, perfume and otheringredients, some degree of dilution without disrupting themicroemulsion, per se, is possible. For example, at the preferred lowlevels of active surfactant compounds (i.e., primary anionic andnonionic detergents) dilutions up to 50% will generally be welltolerated without causing phase separation, that is, the microemulsionstate will be maintained.

In addition to the above-described essential ingredients required forthe formation of the microemulsion composition, the compositions of thisinvention may often and preferably do contain one or more additionalingredients which serve to improve overall product performance.

One such ingredient is an inorganic or organic salt of oxide of amultivalent metal cation, particularly Mg⁺⁺. The metal salt or oxideprovides several benefits including improved cleaning performance indilute usage, particularly in soft water areas, and minimized amounts ofperfume required to obtain the microemulsion state. Magnesium sulfate,either anhydrous or hydrated (e.g., heptahydrate), is especiallypreferred as the magnesium salt. Good results also have been obtainedwith magnesium oxide, magnesium chloride, magnesium acetate, magnesiumpropionate and magnesium hydroxide. These magnesium salts can be usedwith formulations at neutral or acidic pH since magnesium hydroxide willnot precipitate at these pH levels.

Although magnesium is the preferred multivalent metal from which thesalts (inclusive of the oxide and hydroxide) are formed, otherpolyvalent metal ions also can be used provided that their salts arenontoxic and are soluble in the aqueous phase of the system at thedesired pH level.

Thus, depending on such factors as the pH of the system, the nature ofthe primary surfactants and cosurfactant, and so on, as well as theavailability and cost factors, other suitable polyvalent metal ionsinclude aluminum, copper, nickel, iron, calcium, etc. It should benoted, for example, that with the preferred paraffin sulfonate anionicdetergent calcium salts will precipitate and should not be used. It hasalso been found that the aluminum salts work best at pH below 5 or whena low level, for example 1 weight percent, of citric acid is added tothe composition which is designed to have a neutral pH. Alternatively,the aluminum salt can be directly added as the citrate in such case. Asthe salt, the same general classes of anions as mentioned for themagnesium salts can be used, such as halide (e.g., bromide, chloride),sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.

Preferably, in the dilute compositions the metal compound is added tothe composition in an amount sufficient to provide at least astoichiometric equivalent between the anionic surfactant and themultivalent metal cation. For example, for each gram-ion of Mg⁺⁺ therewill be 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate,etc., while for each gram-ion of A1³⁺ there will be 3 gram moles ofanionic surfactant. Thus, the proportion of the multivalent saltgenerally will be selected so that one equivalent of compound willneutralize from 0.1 to 1.5 equivalents, preferably 0.9 to 1.4equivalents, of the acid form of the anionic surfactant. At higherconcentrations of anionic surfactant, the amount of multivalent saltwill be in range of 0.5 to 1 equivalents per equivalent of anionicsurfactant.

The all-purpose liquid cleaning composition of this invention may, ifdesired, also contain other components either to provide additionaleffect or to make the product more attractive to the consumer. Thefollowing are mentioned by way of example: Colors or dyes in amounts upto 0.5% by weight; bactericides in amounts up to 1% by weight;preservatives or antioxidizing agents, such as formalin,5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one,2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pHadjusting agents, such as sulfuric acid or sodium hydroxide, as needed.Furthermore, if opaque compositions are desired, up to 4% by weight ofan opacifier may be added.

In final form, the all-purpose hard surface liquid cleaning compositionsand clear microemulsions exhibit stability at reduced and increasedtemperatures. More specifically, such compositions remain clear andstable in the range of 5° C. to 50° C., especially 10° C. to 43° C. Suchcompositions exhibit a pH in the acid or neutral range depending onintended end use. The liquids are readily pourable and exhibit aviscosity in the range of 6 to 60 milliPascal second (mPas.) as measuredat 25° C. with a Brookfield RVT Viscometer using a #1 spindle rotatingat 20 RPM. Preferably, the viscosity is maintained in the range of 10 to40 mPas.

The compositions are directly ready for use or can be diluted as desiredand in either case no or only minimal rinsing is required andsubstantially no residue or streaks are left behind. Furthermore,because the compositions are free of detergent builders such as alkalimetal polyphosphates they are environmentally acceptable and provide abetter "shine" on cleaned hard surfaces.

When intended for use in the neat form, the liquid compositions can bepackaged under pressure in an aerosol container or in a pump-typesprayer for the so-called spray-and-wipe type of application.

Because the compositions as prepared are aqueous liquid formulations andsince no particular mixing is required to form the microemulsion, thecompositions are easily prepared simply by combining all the ingredientsin a suitable vessel or container. The order of mixing the ingredientsis not particularly important and generally the various ingredients canbe added sequentially or all at once or in the form of aqueous solutionsof each or all of the primary detergents and cosurfactants can beseparately prepared and combined with each other and with the perfume.The magnesium salt, or other multivalent metal compound, when present,can be added as an aqueous solution thereof or can be added directly. Itis not necessary to use elevated temperatures in the formation step androom temperature is sufficient.

The instant microemulsion formulas explicitly exclude alkali metalsilicates and alkali metal builders such as alkali metal polyphosphates,alkali metal carbonates, alkali metal phosphonates and alkali metalcitrates because these materials, if used in the instant composition,would cause the composition to have a high pH as well as leaving residueon the surface being cleaned.

The instant microemulsion and all purpose cleaning composition of theinstant invention do not contain a fatty acid or an alkali metal salt ofa fatty acid (fatty acid soap), or a C₄₋₁₂ alcohol ester of asulfosuccinic acid salt and the compositions are pourable and have astorage modulus of less than 0.5 Pascal (0.5 Newton/sg.m.), whenmeasured at 25° C., at a frequency of ten radians/second and a stream of0.01 and the compositions are not liquid crystals.

It is contemplated within the scope of the instant invention that theinstant partially esterified ethoxylated polyhydric alcohol compound canbe employed in hard surface cleaning compositions such as wood cleaners,window cleaners and light duty liquid cleaners.

The following examples illustrate liquid cleaning compositions of thedescribed invention. Unless otherwise specified, all percentages are byweight. The exemplified compositions are illustrative only and do notlimit the scope of the invention. Unless otherwise specified, theproportions in the examples and elsewhere in the specification are byweight.

EXAMPLE 1

The following composition in wt. % was prepared by simple mixing at 25°C.:

    ______________________________________                   A     B       C      D    ______________________________________    Sodium C.sub.13 -C.sub.17 Paraffin sulfonate                     3       3       4.7  3    Silicone antifoam agent (TP305)                     --      0.04    --   0.02    Ethoxylated nonionic surfactant                     2       2       --   2    C.sub.9-11 EO:5:1    Levenol F-200    2       2       2.3  2    Fatty acid       --      --      0.7  --    DEGMBE           6       6       4    6    MgSO.sub.4 7 H.sub.2 O                     1.12    1.12    2.2  1.12    Perfume (a)      0.8     0.8     0.8  0.8    Water            Bal.    Bal.    Bal  Bal.    pH               7       7       7    7    Degreasing test    Neat (b)         25      25      20   25    Dilute (b)       30      30      40   30    Foam collapse versus Reference                     Worse   Better  REF. Sl. Worse    Residue/Shine versus Reference                     Better  Better  REF. Better    ______________________________________     (a) contains 25% by weight of terpenes.     (b) the lower the number of strokes, the better the degreasing     performance.

The drying time of the compositions are set forth in FIG. 1.

In summary, the described invention broadly relates to an improvement inmicroemulsion and all purpose hard surface cleaning compositionscontaining an anionic surfactant, and/or a partially esterifiedethoxylated polyhydric alcohol and/or an ethoxylated nonionicsurfactant, a cosurfactant, a hydrocarbon ingredient and water.

What is claimed:
 1. A cleaning composition comprising:(a) 0.1 to 10 wt.% of an ethoxylated nonionic surfactant formed from the condensationproduct of ethylene oxide and an alkanol having 8 to 18 carbon atoms oran alkyl phenol having 8 to 18 carbon atoms; (b) 0.1 wt. % to 20 wt. %of an anionic surfactant; (c) 0.1 wt. % to 10 wt. % of a mixture of:##STR6## wherein w equals one to four, and B is selected from the groupconsisting of hydrogen and a group represented by: ##STR7## wherein R isselected from the group consisting of alkyl group having 6 to 22 carbonatoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at leastone of the B groups is represented by said ##STR8## R' is selected fromthe group consisting of hydrogen and methyl groups; x, y and z have avalue between 0 and 60, provided that (x+y+z) equals 2 to 100, whereinin Formula (I) the weight ratio of monoester/diester/triester is 40 to90/5 to 35/1 to 20, wherein the weight ratio of Formula (I) and Formula(II) is a value between 3 and 0.02; (d) 0 to 10 wt. % of a waterinsoluble hydrocarbon, essential oil or a perfume; (e) 0.1% to 15% of aglycol ether cosurfactant; (f) 0.01% to 0.2% of a silicone antifoamagent which is a polyalkylene oxidimethyl siloxane wherein the alkylenegroup has 2 to 40 carbon atoms; and (g) the balance being water, whereinthe composition does not contain a fatty acid, a metal salt of a fattyacid or a C₄₋₁₂ alcohol ester of a sulfosuccinic acid salt.
 2. Thecleaning composition of claim 1 which further contains a salt of amultivalent metal cation in an amount sufficient to provide from 0.5 to1.5 equivalents of said cation per equivalent of said anionicsurfactant.
 3. The cleaning composition of claim 2 wherein themultivalent metal cation is magnesium or aluminum.
 4. The cleaningcomposition of claim 1 wherein the anionic surfactant is a C₉ -C₁₅ alkylbenzene sulfonate or a C₁₀ -C₂₀ alkane sulfonate.
 5. The cleaningcomposition of claim 1, wherein the concentration of the water insolublehydrocarbon, essential oil or perfume is about 0.1 wt. % to about 10 wt.%.